EP0591059A1 - Use of sulfur-containing metaphenylenediamines for dyeing keratinic fibers and new sulfur-containing metaphenylenediamines - Google Patents

Abstract

The invention relates to the use, in dyeing keratinous fibres, of at least one sulphur-containing meta-phenylenediamine of general formula: <IMAGE> in which, Z is alkyl, aralkyl, monohydroxyalkyl, polyhydroxyalkyl, aryl, aminoalkyl or fluoroalkyl, R1 and R2, which are identical or different, are hydrogen, alkyl, monohydroxyalkyl, polyhydroxyalkyl, monocarbamoylalkyl, dialkylcarbamoyl, aminoalkyl, acylaminoalkyl, carbalkoxyalkyl, carbamoyl, monoalkylcarbamoyl or fluoroalkyl, R3 is hydrogen or alkyl, R4 and R5, which are identical or different, are hydrogen, halogen, alkoxy, hydroxyalkyl or -SZ, Z having the above meanings, and the corresponding acid salts, at least one of R3, R4 or R5 is other than hydrogen. The invention also relates to a dyeing composition, to a dyeing process and to new sulphur-containing meta-phenylenediamines.

Description

The present invention relates to the use for dyeing keratin fibers and more particularly human hair, of sulfur-containing metaphenylenediamines, to dye compositions containing these sulfur-containing metaphenylenediamines, to a dyeing process using these compositions, as well as to new sulfur metaphenylenediamines and their process of preparation.

Sulfur derivatives of aromatic amines, associated with oxidation dye precursors, have already been used for dyeing keratin fibers.

It is known to dye keratin fibers and in particular human hair, with dye compositions containing precursors of oxidation dyes and couplers.

The couplers, also called coloring modifiers, make it possible to vary the shades obtained with the precursors of oxidation dyes.

In the field of dyeing keratin fibers and in particular human hair, we are looking for couplers which, associated with precursors of oxidation dyes, make it possible to obtain a wide range of shades, while giving the hair a coloring having a satisfactory resistance to light, washing, weathering, perspiration and the various treatments which the hair may undergo.

The Applicant has just discovered, which is the subject of the invention, that the use of certain sulfur-containing metaphenylenediamines as couplers with oxidation dye precursors of ortho and / or para type and an oxidizing agent in dye compositions for keratin fibers, made it possible to obtain, after application to keratin fibers and in particular human hair, a wide range of coloring shades having resistance to light, washing, weathering, perspiration and various treatments that can undergo the hair, particularly remarkable.

The present invention therefore relates to the use of sulfur-containing metaphenylenediamines defined below for dyeing keratin fibers and in particular human hair.

Another subject of the invention consists of dyeing oxidation compositions, intended to be used for dyeing keratin fibers and in particular human hair, containing at least one oxidation dye precursor of ortho type and / or para and at least one sulfur metaphenylenediamine of formula (I) defined below.

Another subject of the invention relates to the process for dyeing keratin fibers and in particular human hair, using such a composition mixed with an oxidizing agent.

The invention also relates to new sulfur-containing metaphenylenediamines as well as their preparation process.

Other objects of the invention will appear on reading the description and the examples which follow.

dans laquelle : Z représente un radical alkyle en C₁-C₁₈, un radical aralkyle dans lequel le radical alkyle est en C₁-C₆, un radical monohydroxyalkyle en C₁-C₆ ou polyhydroxyalkyle C₂-C₆, un radical aryle, un radical fluoroalkyle en C₁-C₄,un radical aminoalkyle de formule :

dans laquelle n est un nombre entier compris entre 1 et 6 inclus; R₆ et R₇, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle en C₁-C₄, hydroxyalkyle en C₁-C₄, acyle en C₁-C₆;
R₁ et R₂, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C₁-C₆, un radical monohydroxyalkyle en C₁-C₆, polyhydroxyalkyle en C₂-C₆, monocarbamylalkyle en C₁-C₆, dialkyl-carbamyle en C₁-C₆, aminoalkyle en C₁-C₆, acylaminoalkyle (C₁-C₄), carbalcoxy (C₂-C₆) alkyle (C₁-C₄), carbamyle ou monoalkyl en C₁-C₆ carbamyle, fluoroalkyle en C₁-C₄;
R₃ représente un atome d'hydrogène, un radical alkyle en C₁-C₄;
R₄ et R₅, identiques ou différents, représentent un atome d'hydrogène, un radicale alkyle en C₁-C₄, un radical alcoxy en C₁-C₄, un radical hydroxyalkyle en C₁-C₄, un halogène, un radical -SZ où Z a les significations indiquées ci-dessus,
au moins un des radicaux R₃, R₄ ou R₅ est différent d'un atome d'hydrogène,
et leurs sels d'acides.A subject of the present invention is therefore the use for the dyeing of keratin fibers and in particular human hair of at least one sulfur metaphenylenediamine of general formula:

in which: Z represents a C₁-C₁₈ alkyl radical, an aralkyl radical in which the C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl or C₂-C₆ polyhydroxyalkyl radical, an aryl radical, a C₁- fluoroalkyl radical C₄, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive; R₆ and R₇, identical or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₁-C₆ acyl radical;
R₁ and R₂, identical or different, represent a hydrogen atom, a C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl, C₂-C₆ polyhydroxyalkyl, C₁-C₆ monocarbamylalkyl, C₁-C₆ dialkyl-carbamyl , C₁-C₆ aminoalkyl, (C₁-C₄) acylaminoalkyl, (C₂-C₆) carbalkoxy (C₁-C₄) alkyl, carbamyl or C₁-C₆ monoalkyl carbamyl, C₁-C₄ fluoroalkyl;
R₃ represents a hydrogen atom, a C₁-C₄ alkyl radical;
R₄ and R₅, identical or different, represent a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxy radical, a C₁-C₄ hydroxyalkyl radical, a halogen, a -SZ radical where Z has the meanings indicated above,
at least one of the radicals R₃, R₄ or R₅ is different from a hydrogen atom,
and their acid salts.

lorsque les groupements R₆ et R₇ représentent un radical acyle, celui-ci désigne de préférence les radicaux formyle, acétyle et propionyle.
Lorsque le groupement R₃ désigne un radical alkyle, celui-ci est un radical méthyle, éthyle, n-propyle, isopropyle, n-butyle ou isobutyle.Among the preferred meanings of the radical Z in the sulfur-containing metaphenylenediamines of general formula (I) according to the invention, the C₁-C₁₈ alkyl radical denotes the methyl, ethyl, propyl, butyl, dodecyl, hexadecyl radicals; the aralkyl radical denotes the benzyl radical; the mono or polyhydroxyalkyl radical denotes -CH₂-CH₂OH, -CH₂-CHOH-CH₂-OH, -CH₂-CHOH-CH₃; the aryl radical denotes phenyl; the aminoalkyl radical denotes -CH₂-CH₂-NH₂, -CH₂-CH₂-NHCH₃,
the acylaminoalkyl radical denotes
-CH₂-CH₂-NHCOCH₃; or

when the groups R₆ and R₇ represent an acyl radical, the latter preferably denotes the formyl, acetyl and propionyl radicals.
When the group R₃ denotes an alkyl radical, the latter is a methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl radical.

The corresponding acid salts are preferably chosen from hydrochlorides, sulfates or hydrobromides.

Among the sulfur-containing metaphenylenediarnines of general formula (I), there may be mentioned:
2-methyl-4-methylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 2-methyl-4-methylsulfanyl-benzene-1,3-diamine,
2-ethyl-4-methylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 2-ethyl-4-methylsulfanyl-benzene-1,3-diamine,
4-chloro-6-propylthio-1,3 diamino benzene called according to the IUPAC nomenclature 4-chloro-6-propylsulfanyl-benzene-1,3-diamine,
4,6-bis-methylthio-1, 3-diaminobenzene called according to the IUPAC nomenclature 4,6-bis-methylsulfanyl-benzene-1,3-diamine
4,6-bis-ethylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 4,6-bis-ethylsulfanyl-benzene-1,3-diamine
4,6-bis-trifluoromethylthio-1,3- [N, N'bis (2,2,2trifluoroethyl)] - diamino benzene named according to the IUPAC nomenclature
N, N'-bis- (2,2,2-trifluoro-ethyl) -4,6-bis-trifluoromethylsulfanyl benzene-1,3-diamine
4-methyl-6-methylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 4-methyl-6-methylsulfanyl-benzene-1,3-diamine
4-ethylthio-6-methyl-1,3-diamino benzene called according to the IUPAC nomenclature 4-ethylsulfanyl-6-methyl-benzene-1,3-diamine
4-carboxyethylthio-6-carboxymethylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 3- (2,4-diamino-5-carboxymethylsulfanyl-phenylsulfanyl) -propionic acid
4,6-bis-carboxyethylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 3- [2,4-diamino-5- (2-carboxyethylsulfanyl) -phenylsulfanyl] -propionic acid
2-methyl-4,6-bis-methylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 2-methyl-4,6-bis-methylsulfanyl-benzene-1,3-diamine
4,6-bis-ethylthio-2-methyl-1,3-diaminobenzene called according to the IUPAC nomenclature 4,6-bis-ethylsulfanyl-2-methyl-benzene-1,3-diamine
4,6-bis-propylthio-2-methyl-1,3-diaminobenzene called according to the IUPAC nomenclature 4,6-bis-propylsulfanyl-2-methyl-benzene-1,3-diamine
4-methoxy-6-β-acetylaminoethylthio-1,3diaminobenzene called according to the IUPAC nomenclature N- [2- (2,4-diamino-5-methoxy-phenylsulfanyl) -ethyl] -acetamide
4-methoxy-6-methylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 4-methoxy-6-methylsulfanyl-benzene-1,3-diamine
5-chloro-2-methyl-4-β-acetylaminoethylthio-1,3-diaminobenzene called according to the IUPAC nomenclature
N [2- (2,4-diamino 6-chloro 3-methylphenyl sulfanyl) ethyl] acetamide. 4,6-bis-hydroxyethylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 2- [2,4-diamino-5- (2-hydroxy-ethylsulfanyl) -phenylsulfanyl] -ethanol

The compounds of formula (I) can be used as couplers in the presence of oxidation dye precursors of the ortho and / or para type known in themselves, making it possible to dye the hair by oxidation dyeing, according to a process using an oxidative condensation reaction of the precursors and of the coupler.

Ortho and / or para type dye precursors are compounds which are not dyes in themselves, but which form a dye by an oxidative condensation process, either on themselves or in the presence of a coupler or modifier.

These oxidation dye precursors of ortho or para type are benzene or heterocyclic compounds which comprise two amino or hydroxy and amino functional groups, in ortho or para position with respect to each other.

Precursors of oxidation dyes of the ortho or para type can be chosen from paraphenylenediamines, paraaminophenols, heterocyclic precursors para derived from pyridine, pyrimidine or pyrazole, such as 2,5-diaminopyridine, 2-hydroxy 5-aminopyridine, 2,4,5, 6-tetraaminopyrimidine, 4,5-diamino 1-methylpyrazole, 2-dimethylamino 4,5,6-triaminopyrimidine, orthoaminophenols and so-called "double" bases.

dans laquelle :
R₈, R₉, R₁₀, identiques ou différents, représentent un atome d'hydrogène ou d'halogène, un radical alkyle, un radical alcoxy, un radical carboxy, sulfo ou hydroxyalkyle en C₁-C₄ ;
R₁₁ et R₁₂, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle, hydroxyalkyle, alcoxyalkyle, carbamylalkyle, mésylaminoalkyle, acétylaminoalkyle, uréidoalkyle, carbalcoxyaminoalkyle, sulfoalkyle, pipéridinoalkyle, morpholinoalkyle, ou phényle éventuellement substitué en para par un groupement amino.; ou bien R₁₁ et R₁₂ forment conjointement avec l'atome d'azote auquel ils sont liés, un hétérocycle pipéridino ou morpholino, sous réserve que R₈ ou R₁₀ représente un atome d'hydrogène lorsque R₁₁ et R₁₂ ne représentent pas un atome d'hydrogène, ainsi que les sels de ces composés. Ces radicaux alkyle ou alcoxy ont de préférence 1 à 4 atomes de carbone et désignent notamment les radicaux méthyle, éthyle, propyle, méthoxy et éthoxy.Mention may more particularly be made, as paraphenylenediamines, of the compounds corresponding to formula (III):

in which :
R₈, R₉, R₁₀, identical or different, represent a hydrogen or halogen atom, an alkyl radical, an alkoxy radical, a carboxy, sulfo or C₁-C₄ hydroxyalkyl radical;
R₁₁ and R₁₂, identical or different, represent a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfoalkyl, piperidinoalkyl, morpholinoalkyl, or phenyl group optionally substituted by an amino group. ; or else R₁₁ and R₁₂ form, together with the nitrogen atom to which they are linked, a piperidino or morpholino heterocycle, provided that R₈ or R₁₀ represents a hydrogen atom when R₁₁ and R₁₂ do not represent a hydrogen atom, as well as the salts of these compounds. These alkyl or alkoxy radicals preferably have 1 to 4 carbon atoms and denote in particular the methyl, ethyl, propyl, methoxy and ethoxy radicals.

Among the compounds of formula (III), it is more particularly possible cite paraphenylenediamine, p-toluylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, 2,3-dimethylparaphenylenediamine, 2,6-dimethylparaphenylenediamine, 2,6-diethylparaphenylenediamine, 2-dimethylaraphenylenaphenyleniamen , 2,6-dimethyl 5-methoxyparaphenylenediamine, N, N-dimethylparaphenylenediamine, N, N-diethylparaphenylenediamine, N, N-dipropylparaphenylenediamine, 3-methyl 4-amino N, N-diethylaniline, N, N- di- (β-hydroyyethyl) paraphenylenediamine, 3-methyl 4-amino N, N-di- (β-hydroxyethyl) aniline, 3-chloro 4-amino N, N-di- (β-hydroxyethyl) aniline, 4-amino N, N- (ethyl, carbamylmethyl) -aniline, 3-methyl 4-amino N, N- (ethyl, carbarnylmethyl) aniline, 4-amino N, N- (ethyl, β-piperidinoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-piperidinoethyl) aniline, 4-amino N, N- (ethyl, β-morpholinoethyl) aniline, 3-methyl 4- amino N, N- (ethyl, β-morpholinoethyl) aniline, 4-amino N, N- (ethyl, β-acetylaminoethyl) aniline, 4-amino N- (β-methoxyethyl) aniline, 3-methyl 4- amino N, N- (ethyl, β-acetylaminoethyl) aniline, 4-amino N, N- (ethyl, β-mesylaminoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-mesylaminoethyl) aniline , 4-amino N, N- (ethyl, β-sulfoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-sulfoethyl) aniline, N - [(4'-amino) phenyl] -morpholine, N - [(4'-amino) phenyl] piperidine, 2-hydroxyethylparaphenylenediamine, fluoroparaphenylenediamine, carboxyparaphenylenediamine, sulfoparaphenylenediamine, 2-isopropylparaphenylenediamine, 2-n-propylparaphenylen -propylparaphenylenediamine, 2-hydroxymethylparaphenylenediamine, N, Ndimethyl 3-methyl paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) paraphenylenediamine, N- (dihydroxypropyl) paraphenylenediamine, N-4'-amen nediamine, N-phenylparaphenylenediamine.

These paraphenylenediamines can be used either in the form of the free base, or in the form of salts, such as hydrochloride, hydrobromide or sulfate.

Among the p-aminophenols, mention may be made of p-aminophenol, 2-methyl 4-aminophenol, 3-methyl 4-aminophenol, 2-chloro 4-aminophenol, 3-chloro 4-aminophenol, 2,6-dimethyl 4-aminophenol, 3,5-dimethyl 4-aminophenol, 2,3-dimethyl 4-aminophenol, 2,5-dimethyl 4-aminophenol, 2 -hydroxymethyl 4-aminophenol, 2- (β-hydroxyethyl) 4-aminophenol, 2-methoxy 4-aminophenol, 3-methoxy 4-aminophenol, 3- (β-hydroxyethoxy) 4-aminophenol, 2-methoxymethyl 4-aminophenol, 2-aminomethyl 4-aminophenol, 2-β-hydroxyethylaminomethyl 4-aminophenol, 2-ethoxymethyl 4-aminophenol, 2- (β-hydroxyethoxy) methyl 4-aminophenol.

dans laquelle :
   Z₁ et Z₂, identiques ou différents, représentent des groupements hydroxyle ou NHR₁₇, où R₁₇ désigne un atome d'hydrogène ou un radical alkyle inférieur ;
   R₁₄ et R₁₅, identiques ou différents, représentent soit des atomes d'hydrogène, soit des atomes d'halogène, soit encore des radicaux alkyle ;
   R₁₃ et R₁₆, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle, hydroxyalkyle ou aminoalkyle, dont le reste amino peut être substitué; Y représente un radical pris dans le groupe constitué par les radicaux suivants :

dans lesquels n est un nombre entier compris entre 0 et 8 et m, q et p sont des nombres entiers compris entre 0 et 4, cette base pouvant se présenter également sous forme de ses sels d'addition avec des acides.The so-called "double" bases are bis-phenylalkylenediamines, corresponding to the formula:

in which :
Z₁ and Z₂, identical or different, represent hydroxyl groups or NHR₁₇, where R₁₇ denotes a hydrogen atom or a lower alkyl radical;
R₁₄ and R₁₅, identical or different, represent either hydrogen atoms, or halogen atoms, or also alkyl radicals;
R₁₃ and R₁₆, identical or different, represent a hydrogen atom, an alkyl, hydroxyalkyl or aminoalkyl radical, in which the amino residue may be substituted; Y represents a radical taken from the group consisting of the following radicals:

in which n is an integer between 0 and 8 and m, q and p are integers between 0 and 4, this base can also be in the form of its addition salts with acids.

The above-mentioned alkyl or alkoxy radicals preferably denote a group having 1 to 4 carbon atoms and in particular methyl, ethyl, propyl, methoxy and ethoxy.

Among the compounds of formula (IV) there may be mentioned N, N'-bis- (β-hydroethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino 2-propanol, N, N '-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β- hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- ( 4'-amino 3'-methylphenyl) ethylenediamine.

Among the orthoaminophenols, there may be mentioned more particularly 1-amino-2-hydroxybenzene, 6-methyl 1-hydroxy 2-aminobenzene, 4-methyl 1-amino 2-hydroxybenzene, 4-acetylamino 1-amino 2-hydroxybenzene .

The compounds of formula (I) are applied to keratin fibers and in particular human hair by means of dye compositions which constitute another object of the invention.

The compositions in accordance with the invention contain, in a medium suitable for dyeing, at least one sulfur-containing metaphenylenediamine defined above. The preferred compositions contain at least one sulfur metaphenylenediamine defined above, in combination with at least one oxidation dye precursor as defined above.

The dye compositions in accordance with the invention may also contain, in addition to the coupler corresponding to formula (I) defined above, other couplers known in themselves, such as metadiphenols, metaaminophenols, metaphenylenediamines other than those of formula (I) above, metaacylaminophenols, metaurididophenols, metacarbalcoxyaminophenols, α-naphthol, indole derivatives, couplers having an active methylene group, such as β-ketone compounds, pyrazolones.

Among these couplers, mention may more particularly be made of 2,4-dihydroxyphenoxyethanol, 2,4-dihydroxyanisole, metaaminophenol, resorcinol monomethyl ether, resorcinol, 2-methyl-resorcinol, 2-methyl 5-aminophenol, 2-methyl 5-N- (β-hydroxyethyl) aminophenol, 2-methyl 5-N- (β-mesylaminoethyl) aminophenol, 2,6-dimethyl 3-aminophenol, 6-hydroxybenzomorpholine, 2,4-diaminoanisole , 2,4-diaminophenoxyethanol, 6-aminobenzomorpholine, [2-N- (β-hydroxyethyl) amino 4-amino] -phenoxyethanol, 2-amino 4-N- (β-hydroxyethyl) amino anisole, ( 2,4-diamino) phenyl-β, γ-dihydroxypropylether, 2,4-diaminophenoxyethylamine, 1,3-dimethoxy 2,4-diaminobenzene, 1,3,5-trimethoxy 2,4-diaminobenzene, 1- amino 3,4-methylenedioxybenzene, 1-hydroxy 3,4-methylenedioxybenzene, 2-chloro 6-methyl 3-aminophenol, 2-methyl 3-aminophenol, 2-chloro resorcinol, 6-methoxy 3-hydroxyethylaminoaniline, 1-ethox y 2-bis (β-hydroxyethyl) amino 4-aminobenzene, 3-diethylaminophenol, 1,3-dihydroxy 2-methylbenzene, 1-hydroxy 2,4-dichloro 3-aminobenzene, 4,6-di (hydroxyethoxy ) 1,3-diaminobenzene, 4-methyl 6-ethoxy 1,3-diaminobenzene, 4-chloro 6-methyl 3-aminophenol, 6-chloro 3-trifluoroethylaminophenol, and their salts.

Direct dyes such as dyes can be added to these compositions, as is well known in the state of the art, in particular with a view to nuancing or enriching the colors provided by the oxidation dye precursors. azo, anthraquinone or nitro derivatives of the benzene series.

The set of dye precursors by para and / or ortho type oxidation, as well as the couplers used in the dye compositions in accordance with the invention, preferably represent from 0.3 to 7% by weight relative to the weight of the said composition. The concentration of sulfur-containing metaphenylenediamine compounds of formula (I) can vary between 0.05 and 3.5% by weight of the total weight of the composition.

The dye compositions in accordance with the invention also contain, in their preferred embodiment, surfactants anionic, cationic, nonionic, amphoteric or mixtures thereof, well known in the state of the art.

These surfactants are present in the compositions in accordance with the invention in proportions of between 0.5 and 55% by weight, and preferably between 2 and 50% by weight relative to the total weight of the composition.

These compositions can also contain organic solvents to dissolve the components which are not sufficiently soluble in water. Among these solvents, mention may be made, by way of example, of lower C₁-C₄ alkanols, such as ethanol and isopropanol; glycerol; glycols or glycol ethers such as 2-butoxyethanol, ethylene glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and their mixtures.

The solvents are preferably present in proportions of between 1 and 40% by weight, and in particular between 5 and 30% by weight relative to the total weight of the composition.

The thickening agents which can be added to the compositions in accordance with the invention may be chosen from sodium alginate, gum arabic, optionally crosslinked acrylic acid polymers, cellulose derivatives, heterobiopolysaccharides such as xanthan gum, mineral thickening agents such as bentonite can also be used.

These thickening agents are preferably present in proportions of between 0.1 and 5%, and in particular between 0.2 and 3% by weight relative to the total weight of the composition.

The antioxidant agents which may be present in the compositions are chosen in particular from sodium sulfite, thioglycolic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone and homogentisic acid. These antioxidant agents are present in the composition in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition.

The pH of these compositions is between 3 and 10.5. It is adjusted to the desired value using alkalizing agents well known in the art, such as ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives or hydroxides of sodium and potassium, or conventional acidifying agents, such as mineral or organic acids, such as hydrochloric, tartaric, citric, and phosphoric acids.

These compositions can also contain other cosmetically acceptable adjuvants, such as, for example, penetrating agents, sequestering agents, perfumes, buffers, etc.

The compositions in accordance with the invention can be in various forms, such as in the form of a liquid, cream, gel or in any other form suitable for dyeing keratin fibers and in particular human hair. These compositions can be packaged in aerosol bottles in the presence of a propellant and form foams.

The compounds of formula (I) are used in accordance with the invention according to a process comprising the application to the keratin fibers of the compound of formula (I) and of precursors of ortho and / or para oxidation dyes in the presence of a oxidizing agent.

The dye compositions in accordance with the invention containing a dye precursor by oxidation of the para and / or ortho type and a coupler of formula (I) are used according to a process using the development by an oxidizing agent.

In accordance with this process, the dye composition described above is mixed at the time of use with an oxidizing solution in an amount sufficient to be able to develop a coloring, then the mixture obtained is applied to the keratin fibers and in particular the hair. humans.

The pH of the composition applied to the hair preferably varies between 2 and 13. It is adjusted to the desired value using alkalizing agents well known in the art, such as ammonia, carbonates alkalines, alkanolamines such as mono-, di- and triethanolamine, as well as their derivatives or hydroxides of sodium or potassium or acidifying agents conventional, such as mineral or organic acids, such as hydrochloric, tartaric, citric, phosphoric and sulfonic acids. The oxidizing solution contains, as oxidizing agent, hydrogen peroxide, urea peroxide, persalts, such as ammonium persulfate, organic peracids and their salts or alkali metal bromates. Preferably a solution of hydrogen peroxide at 20 volumes is used.

The mixture obtained is applied to the hair and left to stand for 10 to 40 minutes, preferably 15 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried.

The coupler of formula (I) defined above, can also be used in a multi-step process, consisting in one of the steps, in applying the oxidation dye precursor of the ortho and / or para type or mixing them and, in another step, applying a dye composition containing the coupler of formula (I).

The oxidizing agent can be introduced, just before application, into the composition applied in the second step or else be applied to the keratin fibers themselves, in a third step, the conditions of laying, pH, washing and being identical to those indicated above.

dans laquelle : Z' représente un radical alkyle en C₁-C₁₈, un radical aralkyle dans lequel le radical alkyle est en C₁-C₆, un radical monohydroxyalkyle en C₁-C₆ ou polyhydroxyalkyle C₂-C₆, un radical aryle, un radical fluoroalkyle en C₁-C₄,un radical aminoalkyle de formule :

dans laquelle n est un nombre entier compris entre 1 et 6 inclus; R'₆ et R'₇, identiques aux différents, représentent un atome d'hydrogène ou un radical alkyle en C₁-C₄, hydroxyalkyle en C₁-C₄, acyle en C₁-C₆;
R'₁ et R'₂, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C₁-C₆, un radical monohydroxyalkyle en C₁-C₆, polyhydroxyalkyle en C₂-C₆, monocarbamylalkyle en C₁-C₆, dialkyl-carbamyle en C₁-C₆, aminoalkyle en C₁-C₆, acylaminoalkyle (C₁-C₄), carbalcoxy (C₂-C₆) alkyle (C₁-C₄), carbamyle ou monoalkyl en C₁-C₆ carbamyle, fluoroalkyle en C₁-C₄ ;
R'₃ représente un atome d'hydrogène, un radical alkyle en C₁-C₄;
R'₄ et R'₅, identiques ou différents, représentant un atome d'hydrogène, un halogène, un radical alcoxy en C₁-C₄, hydroxyalkyle en C₁-C₄, un radical -SR avec R représentant un radical hydroxyalkyle en C₁-C₄, polyhydroxyalkyle en C₂-C₆, aralkyle dans lequel le radical alkyle est en C₁-C₆, un radical aryle, un radical aminoalkyle de formule :

dans laquelle n est un nombre entier compris entre 1 et 6 inclus; R'₆ et R'₇ identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle en C₁-C₄, hydroxyalkyle en C₁-C₄ ou acyle en C₁-C₆, sous réserve que R'₄ et R'₅ ne désignent pas simultanément un atome d'hydrogène;
et lorsque un des R'₄ ou R'₅ désigne un atome de chlore, R'₃ représente un radical alkyle.
Parmi les composés répondant à la formule (V) définie ci-dessus on peut citer de préférence :
le 4-méthoxy-6-β-acétylaminoéthylthio -1,3 diaminobenzène dénommé selon la nomenclature IUPAC N-[2-(2,4-diamino-5-méthoxy-phénylsulfanyl-éthyl]-acétamide
le 4-méthoxy-6-méthylthio-1,3-diaminobenzène dénommé selon la nomenclature IUPAC 4-méthoxy-6-méthylsulfanyl-benzène-1,3-diamine
le 5-chloro-2-méthyl-4-β-acétylamonoéthylthio-1,3-diaminobenzène dénommé selon la nomenclature IUPAC
N[2-[2,4-diamino 6-chloro 3-méthylphénylsulfanyl)éthyl] acétamide.Another subject of the invention consists of new sulfur-containing metaphenylenediamines which correspond to the formula:

in which: Z 'represents a C₁-C₁₈ alkyl radical, a radical aralkyl in which the alkyl radical is C₁-C₆, a monohydroxyalkyl radical in C₁-C₆ or polyhydroxyalkyl C₂-C₆, an aryl radical, a fluoroalkyl radical in C₁-C₄, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive; R'₆ and R'₇, identical to the different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₁-C₆ acyl radical;
R'₁ and R'₂, identical or different, represent a hydrogen atom, a C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl radical, C₂-C₆ polyhydroxyalkyl, C₁-C₆ monocarbamylalkyl, dialkyl-carbamyl C₁-C₆, C₁-C₆ aminoalkyl, acylaminoalkyl (C₁-C₄), carbalkoxy (C₂-C₆) alkyl (C₁-C₄), carbamyl or monoalkyl C₁-C₆ carbamyl, fluoroalkyl C₁-C₄;
R'₃ represents a hydrogen atom, a C₁-C₄ alkyl radical;
R'₄ and R'₅, identical or different, representing a hydrogen atom, a halogen, a C₁-C₄ alkoxy radical, C₁-C₄ hydroxyalkyl, a -SR radical with R representing a C₁-C₄ hydroxyalkyl radical , C₂-C₆ polyhydroxyalkyl, aralkyl in which the alkyl radical is C₁-C₆, an aryl radical, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive; R'₆ and R'₇ identical or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl or C₁-C₆ acyl radical, provided that R'₄ and R'₅ do not simultaneously denote a hydrogen atom;
and when one of R'₄ or R'₅ denotes a chlorine atom, R'₃ represents an alkyl radical.
Among the compounds corresponding to formula (V) defined above, it is possible to cite preferably:
4-methoxy-6-β-acetylaminoethylthio -1.3 diaminobenzene called according to the IUPAC nomenclature N- [2- (2,4-diamino-5-methoxy-phenylsulfanyl-ethyl] -acetamide
4-methoxy-6-methylthio-1,3-diaminobenzene called according to the IUPAC nomenclature 4-methoxy-6-methylsulfanyl-benzene-1,3-diamine
5-chloro-2-methyl-4-β-acetylamonoethylthio-1,3-diaminobenzene called according to the IUPAC nomenclature
N [2- [2,4-diamino 6-chloro 3-methylphenylsulfanyl) ethyl] acetamide.

4,6-bis-hydroxyethyl thio-1,3-diarninobenzene called according to the IUPAC nomenclature 2- [2,4-diamino-5- (2-hydroxy-ethylsulfanyl) -phenylsulfanyl] -ethanol

The sulfur-containing metaphenylenediamines of formula (V) or their salts can be prepared according to a multi-step process.

dans laquelle R'₆ et n ont les significations indiquées précédemment dans la formule (V); et R₁₇ représente un atome d'hydrogène ou un radical alkyle en C₁-C₃ ;
dans une deuxième étape, on réduit les substituants nitro du composé de formule (VIII) :

obtenu précédernment pour préparer un composé répondant à la formule (IX) :

dans laquelle Z₁ a la signification indiquée ci-dessus ;
éventuellement, dans une troisième étape, et suivant le composé métaphénylènediamine soufrée de formule (I) que l'on souhaite obtenir, on effectue

• a) soit une mono-substitution des amines aromatiques pour obtenir un composé de formule (V) dans laquelle R'₁ et/ou R'₂ sont différents de H;
• b) soit une hydrolyse acide du composé (IX) dans lequel Z' représente un groupement de formule (VII) pour obtenir le composé de formule (X).
  
  dans laquelle R'₆ et n ont les significations indiquées ci-dessus, R'₆ ne désignant toutefois pas de radical acyle en C₁-C₆,
  les amines nucléaires pouvant être ensuite monosubstituées.
• c) soit on effectue au préalable une substitution de l'amine extranucléaire du composé de formule (IX) pour obtenir le composé de formule (XI)
  
  dans laquelle R'₆ et R'₇ et n ont les significations indiquées ci-dessus, les amines nucléaires pouvant être ensuite monosubstituées.

According to a first process and in a first step, reacting in the presence of a base such as potassium hydroxide or potassium carbonate, 1,3-dichloro 4,6-dinitrobenzene on a thiol of formula (VI):

Z₁-SH (VI)


in which Z₁ represents a C₁-C₁₈ alkyl radical, an aralkyl in which the C₁-C₆ alkyl radical, C₁-C₆ monohydroxyalkyl, C₂-C₆ polyhydroxyalkyl, an aryl radical or a group of formula (VII)

in which R'₆ and n have the meanings indicated above in formula (V); and R₁₇ represents a hydrogen atom or a C₁-C₃ alkyl radical;
in a second step, the nitro substituents of the compound of formula (VIII) are reduced:

obtained previously to prepare a compound corresponding to formula (IX):

in which Z₁ has the meaning indicated above;
optionally, in a third step, and depending on the sulfur-containing metaphenylenediamine compound of formula (I) which is to be obtained,

• a) or a mono-substitution of the aromatic amines to obtain a compound of formula (V) in which R'₁ and / or R'₂ are different from H;
• b) or an acid hydrolysis of the compound (IX) in which Z 'represents a group of formula (VII) to obtain the compound of formula (X).
  
  in which R'₆ and n have the meanings indicated above, R'₆ however not designating a Cyle-C₆ acyl radical,
  the nuclear amines can then be monosubstituted.
• c) either a substitution of the extranuclear amine of the compound of formula (IX) is carried out beforehand to obtain the compound of formula (XI)
  
  in which R'₆ and R'₇ and n have the meanings indicated above, the nuclear amines can then be monosubstituted.

dans laquelle R₁₇ représente un groupement alkyle en C₁-C₄ sur un thiol de formule :

        Z₁ -SM   (XIII)


dans laquelle, M est un métal alcalin et Z₁ a les significations indiquées ci-dessus.According to a second process, and in a first step, a substituted compound of formula (XII) is reacted

in which R₁₇ represents a C₁-C₄ alkyl group on a thiol of formula:

Z₁ -SM (XIII)


in which, M is an alkali metal and Z₁ has the meanings indicated above.

obtenu précédemment pour préparer le composé de formule (XV)

dans laquelle R₁₇ et Z₁ ont les significations indiquées ci-dessus ; éventuellement, dans une troisième étape, et suivant la métaphénylènediamine soufrée de formule (V) que l'on souhaite obtenir, on effectue une monosubstitution de l'amine aromatique pour obtenir un composé de formule (V) dans laquelle R'₁ ou R'₂ est différent de H.In a second step, the nitro substituent of the compound of formula (XIV) is reduced

obtained previously to prepare the compound of formula (XV)

in which R₁₇ and Z₁ have the meanings indicated above; optionally, in a third step, and depending on the sulfur metaphenylenediamine of formula (V) which it is desired to obtain, a monosubstitution of the aromatic amine is carried out to obtain a compound of formula (V) in which R'₁ or R ' ₂ is different from H.

sur un thiol de formule :

        Z₁-SM   (XIII)


dans laquelle, M est un métal alcalin et Z₁ a les significations indiquées ci-dessus.According to a third process and in a first step, a polysubstituted 2,4-dinitrobenzene of formula (XVI) is reacted

on a thiol of formula:

Z₁-SM (XIII)


in which, M is an alkali metal and Z₁ has the meanings indicated above.

obtenu précédemment pour préparer un composé répondant à la formule (XVIII).

dans laquelle Z₁ a les significations indiquées ci-dessus.In a second step, the nitro substituents of the compound of formula (XVII) are reduced:

obtained previously to prepare a compound corresponding to formula (XVIII).

in which Z₁ has the meanings indicated above.

The reduction of the nitro groups is preferably carried out using iron in an acetic medium or else by cyclohexene in the presence of a palladium-carbon catalyst or also by zinc powder in the presence of ethanol and ammonium chloride or by any other conventional reduction process.

The substitution of aromatic amines or extra-nuclear amine can be carried out by reacting, for example, ethyl bromide, glycol bromhydrin, ethyl-chloroformate, β-chloroacetamide, or acetic anhydride .

The examples which follow are intended to illustrate the invention without however being limiting in nature.

Preparation example 1 : Preparation of the dihydrochloride, 4-methoxy 6-methylthio 1,3-diaminobenzene monohydrate called according to the IUPAC nomenclature 4-methoxy 6-methylsulfanyl-benzene 1,3-diamine dihydrochloride, monohydrate. 1st step : Synthesis of (5-methoxy 2,4-dinitrophenyl) -methyl-sulfane.

To a suspension of sodium thiomethylate (0.15 mole) in 120 ml of dimethoxyethane at room temperature, a solution of 23.2 g (0.1 mole) of 1-chloro 5-methoxy is added dropwise over one hour. -2,4-dinitro-benzene in 60 ml of dimethoxyethane.

The reaction is exothermic: the temperature is maintained between 23 and 25 °.

At the end of the pouring, the suspension is stirred for half an hour and then poured into 60 ml of ice water. The crystallized precipitate is drained, re-empatée in water, washed with isopropanol and recrystallized from boiling dimethoxyethane.

We obtain yellow crystals (16.9 g) melting at 161 ° C and whose elemental analysis calculated for C₈H₈N₂O₅ S is: VS % H% NOT % O% S% Calculated 39.34 3.30 11.47 32.76 13.13 Find 39.54 3.28 11.44 32.71 13.20

2nd stage : reduction.

A mixture of 2.2 g of ammonium chloride, 16.5 ml of water, 140 ml of 96 ° alcohol and 41 g of zinc in fine powder is heated to reflux of the alcohol. The (5-methoxy 2,4-dinitrophenyl) methyl-sulfane obtained in step 1 (11.0 g-0.045 mol) is added in portions so as to maintain the reflux without heating. The reaction is exothermic.

At the end of the addition, the reflux heating is extended for half an hour. The reaction medium is filtered boiling over 17 ml absolute hydrochloric alcohol about 6 N.

By cooling the filtrate, 4-methoxy 6-methylsulfanyl-benzene-1,3-diamine dihydrochloride, crystallizes from monohydrate.

After wringing and drying under vacuum on potash, 7.0 g of white crystals are obtained, melting with decomposition at 198-203 ° C and whose elemental analysis calculated for C₈H₁₆Cl₂ N₂O₂S is: VS % H% NOT % O% S% cl% Calculated 34.92 5.86 10.18 11.63 11.65 25.77 Find 35.23 5.87 10.23 11.30 11.81 25.63

Preparation example 2 : Preparation of dihydrochloride, 4-methoxy monohydrate 6-β-acetylaminoethylthio 1,3-diaminobenzene called according to the IUPAC nomenclature dihydrochloride N- [2- (2,4-diamino-5-methoxy-phenylsulfanyl) -ethyl] -acetamide monohydrate. 1st step : Synthesis of N- [2- (5-methoxy 2,4-dinitro-phenylsulfanyl) -ethyl] -acetamide.

10 g of potassium hydroxide powder are dissolved in a solution of 19.0 g (0.15 mole) of N- (2-mercapto-ethyl) -acetamide in 100 ml of dimethoxyethane heated to 40 ° C.

After cooling to 15 ° C., a solution of 23.2 g (0.1 mole) of 1-chloro-5-methoxy-2,4-dinitro-benzene in 60 ml is poured in dropwise over thirty minutes. of dimethoxyethane, keeping the temperature between 15 and 20 ° C.

The suspension is stirred for 1 hour then is poured into 500 ml of ice water.

The crystallized precipitate is drained, re-empatée in water then in isopropyl alcohol and recrystallized from boiling 96 ° alcohol.

23.2 g of yellow crystals are obtained, melting at 185 ° C. and whose elemental analysis calculated for C₁₁H₁₃N₃O₆ S is: VS % H% NOT % O% S% Calculated 41.90 4.16 13.33 30.45 10.17 Find 41.94 4.15 13.38 30.54 10.09

2nd step : Reduction

The reduction is carried out according to the procedure described for example 1, step 2.

White crystals of N- [2- (2,4-diamino 5-methoxy-phenylsulfanyl) -ethyl] -acetamide monohydrate dihydrochloride are obtained, melting with decomposition at 183-187 ° C and whose elemental analysis calculated for C₁₁H₂1N₃O₃S cl East : VS % H% NOT % O% S% cl% Calculated 38.16 6.11 12.13 13.86 9.26 20.48 Find 37.83 6.48 11.93 14.12 9.25 20.37

Preparation example 3 : Preparation of 4,6-bis-hydroxyethylthio 1,3-diaminobenzene called according to the nomenclature IUPAC 2- [2,4-diamino 5 (2-hydroxyethylsulfanyl) -phenylsulfanyl] -ethanol. 1st step : Synthesis of 2- [5- (2-hydroxy-ethylsulfanyl) 2,4-dinitro-phenylsulfanyl] -ethanol.

A mixture of 34.5 g of potassium carbonate, 8 g of 2-mercaptoethanol and 100 ml of dioxane is heated to 60 ° C.

11.9 g (0.05) of 1.5-2,4-dichloro-dinitro-benzene are added and the heating is continued for 1 hour at 60 ° and then 1 hour at 100 ° C.

The reaction medium is poured into 500 ml of ice water. The crystallized precipitate is drained, re-empatée in water and dried under vacuum on phosphoric anhydride.

After recrystallization, 9.0 g of orange-yellow crystals are obtained, melting at 149 ° C.

2nd floor : Reduction

The reduction is carried out according to the procedure described for Example 1, step 2.

White crystals (81%) of 2- [2,4-diamino-5- (2-hydroxy-ethylsulfanyl) -phenylsulfanyl] -ethanol are obtained, melting at 144 ° C. and whose elemental analysis calculated for C₁₀H₁₆N₂O₂S₂ is: VS % H% NOT % O% S% Calculated 46.13 6.19 10.76 12.29 24.63 Find 46.21 6.07 10.67 12.42 24.57

Preparation example 4 : Preparation of 5-chloro 2-methyl 4-β-acetaminoethylthio 1,3-diaminobenzene called according to the IUPAC nomenclature N- [2- (2,4-diamino 6-chloro 3-methyl-phenylsulfanyl) -ethyl] -acetamide. 1st step: Synthesis of N- [2- (6-chloro 3-methyl 2,4-dinitrophenylsulfanyl) -ethyl] -acetamide.

This synthesis is carried out according to the procedure described for Example 2, step 1. Starting from 30.1 g (0.12 mole) of 1,2-dichloro-4-methyl 3,5-dinitro-benzene, we obtains 15.5 g of pale yellow crystals melting at 152 ° C. (recrystallized from ethyl acetate) and whose elemental analysis calculated for C₁₁H₁₂Cl N₃OS is: VS % H% NOT % O% S% Cl% Calculated 39.59 3.62 12.59 23.97 9.61 10.62 Find 39.67 3.62 12.63 23.84 9.69 10.56

2nd step : Reduction

The reduction is carried out according to the procedure described for Example 1, step 2.

We obtain white crystals (recrystallized from 96 ° ethanol) of N- [2- (2,4-diamino 6-chloro 3-methyl-phenylsulfanyl) -ethyl] acetamide melting at 111 ° C and whose elemental analysis calculated for C₁₁H₁₆ Cl N₃ OS is: VS % H% NOT % O% S% Cl% Calculated 48.26 5.89 15.35 5.84 11.71 12.95 Find 48.31 5.92 15.27 5.92 11.69 12.87

Examples of compositions EXAMPLE 1

• Dichlorhydrate, monohydrate de 4-méthoxy 6-β-acétylaminoéthylthio 1,3-diaminobenzène   1,038 g
• Dichlorhydrate de 2,6-diméthyl paraphénylènediamine   0,627 g
• Alcool oléique polyglycérolé à 2 moles de glycérol   4 g
• Alcool oléique polyglycérolé à 4 moles de glycérol   5,7 g
• Acide oléique   3 g
• Amine oléique oxyéthylénée à 2 moles d'oxyde d'éthylène commercialisé sous la dénomination ETHOMEEN O12 par la Société AKZO   7 g
• Sel de sodium du laurylamino succinamate de diéthylaminopropyle   3 g MA
• Alcool oléique   5 g
• Diéthanolamide d'acide oléique   12 g
• Propylène glycol   3,5 g
• Alcool éthylique   7 g
• Dipropylène glycol   0,5 g
• Monométhyléther de propylène glycol   9 g
• Métabisulfite de sodium en solution aqueuse à 35 %   0,45 g MA
• Acétate d'ammonium   0,8 g
• Antioxydant, séquestrant   q.s
• Parfum, conservateur   q.s
• Monoéthanolamine   q.s.   pH : 9,8
• Eau déminéralisée   q.s.p.   100 g

Au moment de l'emploi, on mélange la composition ci-dessus, poids pour poids, avec de l'eau oxygénée à 20 volumes dont le pH est ajusté entre 1 et 1,5 par addition d'acide orthophosphorique. Le pH du mélange est égal à 6,5. Celui-ci est appliqué sur des cheveux gris à 90 % de blancs pendant 30 minutes à température ambiante. Les cheveux sont ensuite rincés, lavés au shampooing, rincés une nouvelle fois puis séchés. Ils sont colorés en bleu.

• Hydrochloride, 4-methoxy 6-β-acetylaminoethylthio 1,3-diaminobenzene monohydrate 1.038 g
• 2,6-dimethyl paraphenylenediamine dihydrochloride 0.627 g
• Polyglycerolated oleic alcohol with 2 moles of glycerol 4 g
• Polyglycerolated oleic alcohol with 4 moles of glycerol 5.7 g
• Oleic acid 3 g
• Oxyethylenated oleic amine containing 2 moles of ethylene oxide marketed under the name ETHOMEEN O12 by the company AKZO 7 g
• Sodium salt of diethylaminopropyl laurylamino succinamate 3 g MA
• Oleic alcohol 5 g
• Oleic acid diethanolamide 12 g
• Propylene glycol 3.5 g
• Ethyl alcohol 7 g
• Dipropylene glycol 0.5 g
• Propylene glycol monomethyl ether 9 g
• Sodium metabisulfite in 35% aqueous solution 0.45 g MA
• Ammonium acetate 0.8 g
• Antioxidant, sequestering qs
• Perfume, preservative qs
• Monoethanolamine qs pH: 9.8
• Demineralized water qs 100 g

At the time of use, the above composition, weight for weight, is mixed with hydrogen peroxide at 20 volumes, the pH of which is adjusted between 1 and 1.5 by addition of orthophosphoric acid. The pH of the mixture is 6.5. This is applied to gray hair with 90% white for 30 minutes at room temperature. The hair is then rinsed, washed with shampoo, rinsed again and then dried. They are colored blue.

EXAMPLE 2

It is similar to Example 1 except that the 1.038 g of dihydrochloride, 4-methoxy-6-β-acetylaminoethylthio 1,3-diaminobenzene monohydrate is replaced by 0.821 g of 5-chloro 2-methyl 4 -β-acetylaminoethylthio 1,3-diaminobenzene.
The dyeing conditions are identical to those described in Example 1. The gray hair with 90% white is colored golden mat.

EXAMPLE 3

• Dichlorhydrate, monohydrate de 4-méthoxy 6-méthylthio   0,55 g
  1,3-diaminobenzène
• Paraphénylènediamine   0,216 g
• Octyldodécanol vendu sous la dénomination EUTANOL D   8 g
  par la Société HENKEL
• Alcool oléique   20 g
• Lauryléthersulfate de monoéthanolamine vendu sous la dénomination SIPON LM 35 par la Société HENKEL   3 g
• Alcool éthylique   10 g
• Alcool benzylique   10 g
• Alcool cétylstéarylique oxyéthyléné à 33 moles d'oxyde d'éthylène vendu sous la dénomination SIMULSOL GS par la société SEPPIC   2,4 g
• Acide éthylène diamine tétracétique   0,2 g
• Solution de polymère cationique comportant les motifs suivants :
  
  à 60 % de M.A.   3,7 g
• Monoéthanolamine   7,5 g
• Diéthanolamide d'acide linoléique vendu sous la dénomination COMPERLAN F par la Société HENKEL   8 g
• Ammoniaque à 20 % de NH3   10,2 g
• Métabisulfite de sodium en solution aqueuse à 35 %   1,3 g
• Hydroquinone   0,15 g
• 1-phényl 3-méthyl 5-pyrazolone   0,2 g
• Eau déminéralisée   qs.p.   100 g

Cette composition est mélangée au moment de l'emploi, poids pour poids, avec de l'eau oxygénée à 20 volumes dont le pH est égal à 3. Le pH du mélange est égal à 9,5. Celui-ci est appliqué sur des cheveux gris permanentés pendant 30 minutes à température ambiante. Les cheveux sont ensuite rincés, lavés au shampooing et séchés. Ils sont colorés en gris bleuté mât. The following tintorial composition is prepared:

• Hydrochloride, 4-methoxy 6-methylthio monohydrate 0.55 g
  1,3-diaminobenzene
• Paraphenylenediamine 0.216 g
• Octyldodecanol sold under the name EUTANOL D 8 g
  by the company HENKEL
• Oleic alcohol 20 g
• Monoethanolamine lauryl ether sulfate sold under the name SIPON LM 35 by the company HENKEL 3 g
• Ethyl alcohol 10 g
• Benzyl alcohol 10 g
• Cetylstearyl alcohol oxyethylenated with 33 moles of ethylene oxide sold under the name SIMULSOL GS by the company SEPPIC 2.4 g
• Ethylene diamine tetracetic acid 0.2 g
• Cationic polymer solution comprising the following units:
  
  at 60% MA 3.7 g
• Monoethanolamine 7.5 g
• Diethanolamide of linoleic acid sold under the name COMPERLAN F by the company HENKEL 8 g
• Ammonia at 20% NH3 10.2 g
• Sodium metabisulfite in 35% aqueous solution 1.3 g
• Hydroquinone 0.15 g
• 1-phenyl 3-methyl 5-pyrazolone 0.2 g
• Demineralized water qs.p. 100g

This composition is mixed at the time of use, weight for weight, with hydrogen peroxide at 20 volumes whose pH is equal to 3. The pH of the mixture is equal to 9.5. This is applied to permed gray hair for 30 minutes at room temperature. The hair is then rinsed, washed with shampoo and dried. They are colored in bluish gray mast.

Claims (17)

Use for dyeing keratin fibers, and in particular human hair, of at least one sulfur metaphenylenediamine of general formula:

in which: Z represents a C₁-C₁₈ alkyl radical, an aralkyl radical in which the C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl or C₂-C₆ polyhydroxyalkyl radical, an aryl radical, a C₁ fluoroalkyl radical -C₄, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive, R₆ and R₇, identical or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₁-C₆ acyl radical;
R₁ and R₂, identical or different, represent a hydrogen atom, a C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl radical, C₂-C₆ polyhydroxyalkyl, C₁-C₆ monocarbamylalkyl, dialkyl-carbamyl (C₁-C₆ ), C₁-C₆ aminoalkyl, C₁-C₄ acylaminoalkyl, C₂-C₆ carbalkoxy (C₁-C₄) alkyl, carbamyl or C₁-C₆ carbalk alkyl, C₁-C₄ fluoroalkyl
R₃ represents a hydrogen atom, a C₁-C₄ alkyl radical;
R₄ and R₅, identical or different, represent a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxy radical, C₁-C₄ hydroxyalkyl, a halogen, a -SZ radical where Z has the meanings indicated above, at least one of the radicals R₃, R₄ or R₅ is different from a hydrogen atom and their corresponding acid salts. Use according to claim 1, characterized in that the sulfur-containing metaphenylenediamine of formula (I) is used in the presence of oxidation dye precursors of ortho and / or para type. Use according to claim 1 or 2, characterized in that in the compound of formula (I), Z denotes a methyl, ethyl, propyl, butyl, dodecyl, hexadecyl radical, the benzyl radical, the phenyl radical, a mono or polyhydroxyalkyle chosen from:
-CH₂-CH₂-OH, -CH₂-CHOH-CH₂-OH, -CH₂-CHOH-CH₃, an aminoalkyl radical chosen from:
-CH₂-CH₂NH₂, -CH₂-CH₂-NHCH₃,
an acylaminoalkyl radical chosen from:
-CH₂-CH₂-NH-COCH₃; or

and when R₆ or R₇ denote an acyl radical, this represents a formyl, acetyl or propionyl group. Use according to any one of Claims 1 to 3, characterized in that the compounds of formula (I) are chosen from the following compounds:
2-methyl-4-methylthio-1,3-diaminobenzene
2-ethyl-4-methylthio-1,3-diaminobenzene
4-chloro-6-propylthio-1,3 diamino benzene
4,6-bis-methylthio-1,3-diaminobenzene
4,6-bis-ethylthio-1,3-diaminobenzene
4,6-bis-trifluoromethylthio-1,3- [N, N'-bis- (2 ', 2', 2'-trifluoroethyl)] diamino benzene
4-methyl-6-methylthio -1,3-diaminobenzene
4-ethylthio -6-methyl-1,3-diamino benzene
4-carboxyethylthio 6-carboxymethylthio-1,3-diaminobenzene
4,6-bis-carboxyethylthio 1,3-diaminobenzene
2-methyl 4,6-bis-methylthio 1,3-diaminobenzene
4,6-bis-ethylthio-2-methyl 1,3-diaminobenzene
4,6-bis-propylthio-2-methyl 1,3-diaminobenzene
4-methoxy 6-β-acetylaminoethylthio-1,3-diaminobenzene
4-methoxy 6-methylthio 1,3-diaminobenzene
5-chloro 2-methyl 4-β-acetylaminoethylthio 1,3-diaminobenzene
4,6-bis-hydroxyethyl thio 1,3-diaminobenzene
and their acid salts. Use according to any one of claims 1 to 4, characterized in that the corresponding acid salts are chosen from hydrochlorides, sulfates or hydrobromides. Use according to any one of claims 2 to 5, characterized in that the oxidation dye precursors are chosen from paraphenylenediamines, paraaminophenols, heterocyclic precursors para derived from pyridine, pyrimidine, or pyrazole, orthoaminophenols and bis-phenylalkylenediamines. Dye composition for keratin fibers, and in particular human hair, containing in a medium suitable for dyeing, at least one oxidation dye precursor of ortho and / or para type, and at least, as coupler, a metaphenylenediamine sulfur as defined in claims 1, 3 or 4. Dye composition according to Claim 7, characterized in that it contains other couplers chosen from metadiphenols, metaarninophenols, metaphenylenediamines different from those of formula (I), metaacylaminophenols, metaurideophenols, metacarbalcoxyaminoph enols, α -naphthol, indole derivatives, couplers having an active methylene group. Dye composition according to any one of Claims 7 to 8, characterized in that it contains 0.05 to 3.5% by weight of the total weight of the composition of at least one compound of formula (I). Dye composition according to any one of Claims 7 to 9, characterized in that it contains from 0.3 to 7% by weight relative to the total weight of the composition, of oxidation dye precursors of ortho type and / or para and couplers. Dye composition according to any one of Claims 7 to 10, characterized in that it also contains an adjuvant chosen from cationic, anionic, nonionic, amphoteric surfactants or their mixtures, in concentrations between 0.5% and 55% by weight relative to the total weight of the composition, organic solvents in concentrations of between 1 and 40% by weight relative to the total weight of the composition, direct dyes, thickening agents in concentrations between 0.1 and 5% by weight relative to the total weight of the composition and the antioxidant agents in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition. Dye composition according to any one of Claims 7 to 11, characterized in that it is in the form of a liquid, cream, gel or in any other suitable form, or can be packaged in an aerosol bottle in the presence of a propellant and form foams. Process for the oxidation dyeing of keratin fibers and in particular human hair, characterized in that at least one oxidation dye precursor of the ortho and / or para type and a sulfur metaphenylenediamine is applied to the keratin fibers general formula:

in which: Z represents a C₁-C₁₈ alkyl radical, an aralkyl radical in which the C₁-C₆ alkyl radical, a radical C₁-C₆ monohydroxyalkyl or C₂-C₆ polyhydroxyalkyl, an aryl radical, a C₁-C₄ fluoroalkyl radical, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive, R₆ and R₇, identical or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₁-C₆ acyl radical;
R₁ and R₂, identical or different, represent a hydrogen atom, a C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl, C₂-C₆ polyhydroxyalkyl, C₁-C₆ monocarbamylalkyl, C₁-C₆ dialkyl-carbamyl , C₁-C₆ aminoalkyl, C₁-C₄ acylaminoalkyl, carb (C₂-C₆) alkyl (C₁-C₄), carbamyl or C₁-C₆ monoalkyl carbamyl, Coro-C₄ fluoroalkyl;
R₃ represents a hydrogen atom, a C₁-C₄ alkyl radical,
R₄ and R₅, identical or different, represent a hydrogen atom, a halogen, a C₁-C₄ alkyl radical, C₁-C₄ alkoxy, C₁-C₄ hydroxyalkyl, an SZ radical where Z has the meanings indicated above , provided that at least one of the radicals R₃, R₄, R₅ is different from a hydrogen atom and the corresponding acid salts, in the presence of an oxidizing agent. Process according to Claim 13, characterized in that a dye composition for keratin fibers, and in particular human hair, is mixed at the time of use, containing, in a medium suitable for dyeing, at least one precursor oxidation dye of ortho and / or para type, and at least, as coupler, a sulfur-containing metaphenylenediamine as defined in claim 13, with an oxidizing solution in an amount sufficient to develop the coloration, the resulting composition having a pH varying between 2 and 13, and the mixture is applied in this way obtained on keratin fibers, and in particular human hair. Oxidation dyeing process according to any one of Claims 13 to 14, characterized in that it is left to stand for 10 to 40 minutes, preferably 15 to 30 minutes, the hair is rinsed, it is washed with shampoo, they are rinsed again and dried. New sulfur-containing metaphenylenediamines of general formula:

in which: Z 'represents a C₁-C₁₈ alkyl radical, an aralkyl radical in which the C est-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl or C₂-C₆ polyhydroxyalkyl radical, an aryl radical, a C₁ fluoroalkyl radical -C₄, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive; R'₆ and R'₇, identical to the different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₁-C₆ acyl radical;
R'₁ and R'₂, identical or different, represent a hydrogen atom, a C₁-C₆ alkyl radical, a C₁-C₆ monohydroxyalkyl radical, C₂-C₆ polyhydroxyalkyl, C₁-C₆ monocarbamylalkyl, dialkyl-carbamyl C₁-C₆, C₁-C₆ aminoalkyl, acylaminoalkyl (C₁-C₄), carbalkoxy (C₂-C₆) alkyl (C₁-C₄), carbamyl or monoalkyl C₁-C₆ carbamyl, fluoroalkyl C₁-C₄;
R'₃ represents a hydrogen atom, a C₁-C₄ alkyl radical;
R'4 and R'5, identical or different, representing a hydrogen atom, a halogen a C₁-C₄ alkoxy, C₁-C₄ hydroxyalkyl radical, a -SR radical with R representing a C₁-C₄ hydroxyalkyl radical, C₂-C₆ polyhydroxyalkyl, aralkyl in which the alkyl radical is C₁-C₆, an aryl radical, an aminoalkyl radical of formula:

in which n is an integer between 1 and 6 inclusive; R'₆ and R'₇, identical or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl or C₁-C₆ acyl radical,
provided that R'₄ and R'₅ do not simultaneously denote a hydrogen atom;
and when one of R'₄ or R'₅ denotes a chlorine atom, R'₃ represents an alkyl radical. Sulfurated metaphenylenediamines according to claim 17, characterized in that it is chosen from:
4-methoxy 6-β-acetylaminoethylthio 1,3-diaminobenzene
4-methoxy 6-methylthio 1,3-diaminobenzene
5-chloro 2-methyl 4-β-acetylaminoethylthio 1,3-diaminobenzene
4,6-bis-hydroxyethyl thio 1,3-diaminobenzene